Pigment azo dyestuffs



Patented Nov. 2, 1937 PATENT oFncE PIGMENT AZO DYESTUFFS AugustModersohn, Cologne-Mulheim, and Werner Schleifenbaum,

Leverkusen-I. G.-Werk,

Germany, assignors to General Aniline Works; Inc., New York, N. Y., acorporation of Dela-,

ware

- No Drawing, Application March 11, 1935, Se-

rial No. 10,580. In Germany March 17, 1934 n 4 claims.

The present invention relates to. new pigment dyestuffs-moreparticularly it relates to dyestuffs which may be represented by, thefollowing general formula:

wherein R stands for alkyl, aralkyl or aryl, which radicals may containnon-solubilizing substituents, and x and y stand for hydrogen, alkyl,

alkoxy or halogen, or for aralkyl, aryl, aralkoxy or aryloxy,whichlatter radicals may contain nonsolubilizing substituents in thenucleus,however, 11 can only stand for the same substituent l as if a:standsfor hydrogen or alkyl, 2 stands for alkyl and n stands forawholenumber larger than 1, and wherein two zs in o-position to each other maybe linked up to form a ring.

Our new dyestuffs are obtainable by coupling in substance or on asubstratum of the kind generally used in the manufacture of pigments,such as barium sulfate, the diazo compound of an amine of the generalformula:

: wherein R, a: and :1; mean the same as stated above, with a2,3-hydroxynaphthoic acid anilide, bearing in the benzene nucleus atleast two alkyl groups as substituents.

The new pigment dyestuifs are distinguished by a good fastness to lightcombined with a good fastness to oil, spirit and solvents.

The invention is illustrated by the following examples, without beinglimited thereto:

Example 1.475 grams of2-hydroxynaphthalene-B-carbonylamino-Z,5-dimethylbenzene are dissolvedwith 250 cos. of aqueous concentrated caustic soda. lye with theaddition of a wetting agent, and the solution thus obtained is made upwith water to about 12 litres. Into this solution there is slowlyintroduced with stirring a diazo solution prepared by diazotizing in theusual manner 395 grams of 3-amino-4-methy1diphenylsulfone. The dyestuffformedhaving the following formu1a; i

I w F Q QM CH3 separates in the form of a reddish-orange precipitate. Itcan be used in the paste or powder form and is distinguished by a verygood fastness to oil, spirit and solvents.

' By substituting the -2-hydroxynaphthalene-3-carbonylamino-z!,5-dimethylbenzene by the 2- hydroxynaphthalene- 3-carbony1amino-2',3'-di methylbenzene for2-hydroxynaphthalene-3-carbonylamino-2,4'-dimethylbenzene there areobtained dyestufis of similar shades and similar fastness properties.

Example 2.-110 grams of2-hydroxynaphtha-Iene-B-carbonylamino-Z',4-dimethylbenzene are dissolved in the usualmanner with the aid of caustic soda lye. The solution is made up withwater to 3 litres and after cooling to about 0 C., the naphthol. isreprecipitated by hydrochloric acid, while well stirring. After theaddition of 100 grams of sodium acetate, into the suspension of thenaphthol there is poured a diazo solution prepared in theusual mannerfrom 100 grams of 3-amino-4-methoxyphenylbutylsulfone. The dyestufihaving the following formula:

IOHa

amigos is after drying obtained in form of a dark red pigmentsuitablefor preparing color lakes fast to oil, spirit and solvents.

By substituting the 2-hydroxynaphthalene-3- carbonylamino 2,4dimethylbenzene by an equivalent quantity of 2-hydroXynaphthalene-3-carbonylamino-2',3-dimethylbenzene, there is obtained a pigment ofsimilar shades and having otherwise the same properties.

Example 3.-Into a suspension prepared from 430 grams ofZ-hydroxynaphthalene-3-carb0nylamino-2,4-dimethylbenzene according tothe directions given in Example 2, there is poured after the addition of300 grams of sodium acetate a diazo solution prepared in the usualmanner from 402 grams of 3-amino-4-methoxyphenylbenzylsulfone. ish-redpigment of the formula:

OCHa HO I SO:

practically insoluble in oil, alcohol and the-sobvents used in the artof preparing nitrocellulose lacquers. I

Example 4.-385 grams of 3-amino-4-methoxydiphenylsulfone are diazotizedin the usual manner, and the diazo solution obtained is diluted withwater to 10 litres. Into this solution, after the addition of 800 cos.of glacial acetic acid, there is poured an alkaline reacting-solution of430 grams of Z-hydroxyn-aphthalene-B- carbonylamino-2,3-dimethylbenzene.The dyestuff of the following formula:

H80 on:

00113 HO (IO-NH CaHs ' separates in form of a bluish-red precipitate andis suitable for preparing color lakes fast to 'oil, spirit and solvents.

By substituting the 3-amino-4-methoxydiphenylsulfone by thecorresponding quantity 'of 3 amino 4 methoxy-6-ch1orophenylbenzylsulfoneand the 2-hydroxynaphthalene-3-carbonylamino-2,3'-dimethylbenzene by 2hydroxynaphthalene-3-carbonylamino-2, l dimethylbenzene, there isobtained a dyestuff of similar properties but more bluish shade.

Example 5.320 grams of Z-hydroxynaphthalene-3-carbonyl-1-aminotetrahydronaphthalene are dissolved in 140 cos.of concentrated aqueous caustic soda. lye. After cooling, to about 0 C.the naphthol is precipitated by adding hydrochloric acid until weaklyacid to Congo. To the suspension thus obtained there is added a diazosolution prepared in the usual manner from 200 grams of3-amino-4methyl-phenylethylsulfone and then .500 cos. of pyridine. Thedyestuff having the following formula:

is obtained'in form of ared pigment having the Thus is obtained a clearYBHOW? I .mixture is neutralized with aqueous sodium acetate solution,and after this, a solution of grams of sodium acetate free from water in400 cos. of water is added. The dyestuff having the following formula:

(iJHa N=N CH:

C 'r-CoHs represents after drying a yellowish-red powder. suitable forbeing worked into oil and nitrocel1u-'-' lose lacquers.

In an analogous manner as described above 2-hydroxynaphthalene- 3carbonylamino-2',3- dimethylbenzene yields when coupled with diazotized.3 amino-4-phenoxyphenylethylsulfone of the formula:

or with diazotized 3-amino-4-benzyloxydiphenylsulfone of the formula?red pigments of good fastness properties.

We claim: 1. Pigment dyestuffs of the general formula:

SiOzR wherein R stands for a member selected from the group consistingof alkyl, aralkyl and aryl, :1: and y stand for members selected fromthe group consisting of hydrogen, alkyl, alkoxy, halogen, aralkyl, aryl,aralkoxy and aryloxy in such a manner that 11 only stands for the samevalue as :r, if :0 stands for hydrogen or alkyl, 2 stands for a loweralkyl group and 11. stands for a whole number larger than 1, and suchderivatives thereof in which two zs in o-position to each other form atetramethylene chain, being distinguished by a good fastness to lightcombined with a good fastness to oil, spirit and solvents.

2. The pigment dyestufl of the following being a yellowish-red substanceof a. very good formula: fastness to oil, spirit and solvents. 7

CH: 4. The pigment dyestufi of the following formula: 5 f H0 CO NH" H1Ocm 6 Q OCH: no w-NHO S02 N=N 10 10 being a reddish-orange substance ofa. very good being Substance of very good fastness to oil, spirit andsolvents. fastness Spmt and solvents 15 3. Th 1 formulae p1gmentdyestufi of the fol owmg AUGUST M ODERS OHN.

' OH, WERNER SCHLEIFENBAUM.

( mm no C0-NHO-CHI HrCoHa

